Vasiliy V. Rosen, M.Sc.

, ZBM Analytical Laboratory

icpaes@gmail.com, www.rosen.r8.org
2012
 INTRODUCTION

‫ספקטרוסקופיה בליעה‬ ‫ספקטרוסקופיה פליטה‬

Absorption Spectroscopy: Emission Spectroscopy:
AAS FES, ICP-AES(OES)

‫ספקטרוסקופיה מסה‬
Mass Spectrometry
INTRODUCTION

Ion Emission

Atom Emission

E – energy difference between two levels;

h – Plank’s constant, 6.626068 × 10-34 m2kg/s;
c – speed of light, 299 792 458 m/s;
λ – wavelenght, nm
 INTRODUCTION

Nebulizer converts the

solution into a spray

Flame (or Plasma) causes the solvent to evaporate,

leaving dry aerosol particles, then volatilizes the particles,
producing atomic, molecular and ionic species
 SAMPLE PREPARATION

Process Goal Problems

Drying Sample stabilization, Thermal

homogenization and decomposition and
accurate weighing reduction in dry
facilitation weight

Grinding Sample homogenization, Pollution by metals

organic matter reduction from the mill parts
facilitation

Dry or Wet Acid Organic matter destruction, Analyte loss,

Digestion solid material dissolution contamination, not
complete solid
dissolution
 SAMPLE PREPARATION EQUIPMENT

Microwave-assisted Digestion

Hot Plate Digestion Block

Most samples have to be prepared for analysis on ICP, FF and AA. Solid samples are
solubilized. Organic matter is "mineralized" i.e. converted to inorganic compounds.
SAMPLE PREPARATION EQUIPMENT

Microwave Laboratory Oven “Ethos One”

and Teflon vessels
SAMPLE PREPARATION EQUIPMENT

“Ethos One”: Temperature and Pressure control

SAMPLE PREPARATION EQUIPMENT

“Ethos One”: “Vent-and-Reseal” technology

 SAMPLE PREPARATION EQUIPMENT
6 samples

250 1200
1000
Temperature (°C)

200

Power (watt)
800
150
600
100
400
50 200
0 0
0.00 0.05 0.10 0.15 0.20 0.25
Time (minutes)

“Ethos One”: Digestion profile

 MATRIX

Cd, 1 mg/L, in weak acid

Cd, 1 mg/L, in base

Analyte concentrations are equal, but intensities are different

11
 MATRIX
The elements that are stable/soluble in HNO3
 MATRIX
The elements that are stable/soluble in HCl
 MATRIX

The elements that are stable/soluble in H2SO4

 MATRIX

HNO3

HCl

H2SO4
 QC PROCEDURES

Replicates – method precision * evaluation.

Spike – addition of the known concentration of

analyte to the sample at the preparation step. The
evaluation of the preparation quality and matrix effect.

Matrix matching – preparation of the calibration

standards in the same matrix as the samples.

Internal standard – addition of the element that

sample does not contain (Y, Sc) in known
concentration. The evaluation of the matrix effect.

Standard Reference Material preparation and

analysis for method accuracy ** evaluation.
*Precision is how close the measured values are to each other.
**Accuracy is how close a measured value is to the actual (true) value.
 QC PROCEDURES
SRM 1570a Spinach Leaves Elemental Analysis

Method precision Method accuracy

FLAME EMISSION SPECTROSCOPY (FES)

 Propane-butane flame ( 2000 – 3000 º C);

 Optical filter is used to monitor for the selected emission wavelength
produced by the analyte;
 Suitable for elements with low excitation energy (Na, K, Li, Rb, Cs and Ca).
FLAME EMISSION SPECTROSCOPY (FES)
Optic Filter
Flame

Data Display

Nebulizer

Flame Photometer M-410

(Sherwood Scientific, UK)
FLAME EMISSION SPECTROSCOPY (FES)
FLAME EMISSION SPECTROSCOPY (FES)
ATOMIC ABSORPTION SPECTROSCOPY (AAS)

 Gases mixture flame (1800 – 4500 º C): air-propane, air-acetylene etc. ;

 Atomic absorption spectrometry quantifies the absorption of ground state atoms in the
gaseous state ;
 The atoms absorb ultraviolet or visible light and make transitions to higher electronic
energy levels . The analyte concentration is determined from the amount of absorption.
ATOMIC ABSORPTION SPECTROSCOPY (AAS)
Operation principle of AAS

Light source – hollow cathode lamp. Each element has its own unique lamp.
Atomic cell – flame (gas mixture) or graphite furnace (accepts solutions, slurries, or even
solids).
Detector – photomultiplier.
ATOMIC ABSORPTION SPECTROSCOPY (AAS)
ATOMIC EMISSION SPECTROSCOPY

ICP-AES
Inductively Coupled Plasma -

Atomic Emission Spectrometry

 ICP-AES
Basics
Atomic emission spectroscopy measures the intensity of
light emitted by atoms or ions of the elements of interest at
specific wavelengths;
Inductively Coupled Plasma spectrometers use emission
spectroscopy to detect and quantify elements in a sample;
 ICP-AES uses the argon plasma (6000-10000º C) for
atomization and excitation of the sample atoms;
 ICP-AES determines approximately all of the elements
except gases and some non-metals (C, N, F, O, H).
ICP-AES SPECTROMETER ARCOS
Schematic diagram of the processes in the ICP
ICP SPECTROMETER
Main Systems
ICP-AES: SAMPLE INTRODUCTION SYSTEM

Torch with Plasma

Nebulizer (cross-flow)
Spray Chamber

To Waste

Sample
Solution
Entrance
Argon Supply
 ICP-AES: NEBULIZER

Cross-flow nebulizer Modified-Lichte nebulizer

Burgener nebulizer
ICP-AES: NEBULIZER

aerosol
ICP-AES: NEBULIZER

Modified Lichte Nebulizer

aerosol
ICP-AES: NEBULIZER

aerosol
ICP-AES: TORCH

Auxiliary
Argon Flow

Coolant
Argon Flow

Nebulizer
Argon Flow
ICP-AES: TORCH
 ICP-AES: PLASMA
Inductively Coupled Plasma Source
A plasma is a hot, partially ionized
gas. It contains relatively high
concentrations of ions and electrons.

Argon ions, once formed in a plasma, are

capable of absorbing sufficient power from
an external source to maintain the
temperature at a level at which further
ionization sustains the plasma indefinitely.
The plasma temperature is about 10 000 K.
ICP-AES: PLASMA
Inductively Coupled Plasma Source
ICP-AES: RADIAL (SOP) AND AXIAL (EOP)
 ICP-AES: RADIAL (SOP) AND AXIAL (EOP)

SOP: Side-on-Plasma EOP: End-on-Plasma

 more suitable for hard matrices (concentrated samples);  more suitable for light matrices;
 alkali metals (Na, K, Li) calibration is more linear;  alkali metals (Na, K, Li) calibration is less linear;
 less spectral interferences;  more spectral interferences;
lower sensitivity (Limit-of-Detection is higher); higher sensitivity (Limit-of-Detection is lower);
ICP-AES: OPTICS
ICP-AES: OPTICS
ICP-AES: BACKGROUND CORRECTION

Background Correction Background Correction

Position 1 Position 2

Linear Function Approximation

ICP-AES: BACKGROUND CORRECTION

Linear Function
Approximation

Polynomial Function
Approximation
ICP-AES: SPECTRAL INTERFERENCES

Sulfur in plant sample Boron in plant sample

Boron in plant sample

Boron in standard
Sulfur in standard
(1 mg/L)
(10 mg/L)

Sulfur spectral interference on Boron line 182.6 nm

ICP-AES: SPECTRAL INTERFERENCES

Fe 25 ppm Iron spectral

interference on
B 0.1 ppm
Boron lines 249.7
and 208.8 nm

Fe 25 ppm
ICP-AES: SPECTRAL INTERFERENCES
Manganese spectral interference on Gold lines 242.7 mn

Mn 10 ppm

Numerical Data

Au 1 ppm
ICP-AES: CALIBRATION CURVE
 ICP-MS: BASICS

Shadow stop blocks

the photons

(+)
(+) (+)
(+)

Electrostatic lens
focuses the beam
into the slit

Cones sample the center

portion of the ion beam
 ICP-MS: BASICS

Quadropole mass filter can

separate up to 2400 amu (atomic
mass units) per second by switching
alternating voltages applied to
opposite pairs of the rod
ICP-MS: BASICS
ICP-MS: BASICS
ICP-MS: BASICS
 ICP-AES (MS), FES AND AAS: APPLICATION

 Clinical Analysis: metals in biological fluids (blood, urine);

 Environmental Analysis: trace metals and other elements in waters, soils, plants,

composts and sludges;

 Pharmaceuticals: traces of catalysts used; traces of poison metals (Cd, Pb etc);

 Industry: trace metal analysis in raw materials; noble metals determination.

 Forensic science: gunshot powder residue analysis, toxicological examination

( e.g., thallium (Tl) determination)

ZBM LABORATORY WEBSITE

http://departments.agri.huji.ac.il/zabam/